EP2093242A1 - Group 3 post-metallocene complexes based on bis (Naphthoxy)pyridine and bis (Naphthoxy) thiophene ligands for the ring-opening polymerisation of polar cyclic monomers - Google Patents

Group 3 post-metallocene complexes based on bis (Naphthoxy)pyridine and bis (Naphthoxy) thiophene ligands for the ring-opening polymerisation of polar cyclic monomers Download PDF

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Publication number
EP2093242A1
EP2093242A1 EP08290186A EP08290186A EP2093242A1 EP 2093242 A1 EP2093242 A1 EP 2093242A1 EP 08290186 A EP08290186 A EP 08290186A EP 08290186 A EP08290186 A EP 08290186A EP 2093242 A1 EP2093242 A1 EP 2093242A1
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EP
European Patent Office
Prior art keywords
group
bis
naphthoxy
thf
alkyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
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EP08290186A
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German (de)
English (en)
French (fr)
Inventor
Jean-François Carpentier
Evgueni Kirillov
Abbas Razavi
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Total Petrochemicals Research Feluy SA
Centre National de la Recherche Scientifique CNRS
Original Assignee
Total Petrochemicals Research Feluy SA
Centre National de la Recherche Scientifique CNRS
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Application filed by Total Petrochemicals Research Feluy SA, Centre National de la Recherche Scientifique CNRS filed Critical Total Petrochemicals Research Feluy SA
Priority to EP08290186A priority Critical patent/EP2093242A1/en
Priority to CN2009801064101A priority patent/CN101959928B/zh
Priority to EP09714063A priority patent/EP2247641A1/en
Priority to KR1020107018747A priority patent/KR101217954B1/ko
Priority to US12/919,256 priority patent/US8436133B2/en
Priority to BRPI0907927-0A priority patent/BRPI0907927A2/pt
Priority to EA201070998A priority patent/EA018583B1/ru
Priority to PCT/EP2009/051869 priority patent/WO2009106459A1/en
Publication of EP2093242A1 publication Critical patent/EP2093242A1/en
Priority to US13/847,215 priority patent/US20130281681A1/en
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C08G63/82—Preparation processes characterised by the catalyst used
    • C08G63/84—Boron, aluminium, gallium, indium, thallium, rare-earth metals, or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C08G63/82—Preparation processes characterised by the catalyst used
    • C08G63/823—Preparation processes characterised by the catalyst used for the preparation of polylactones or polylactides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/20—General preparatory processes
    • C08G64/30—General preparatory processes using carbonates

Definitions

  • the present invention relates to the use of group 3 post-metallocene complexes based on sterically encumbered bis(naphthoxy)pyridine and bis(naphthoxy)thiophene ligands in the ring-opening polymerisation of polar cyclic monomers such as, for examples, lactones, lactides, and cyclic carbonates.
  • polyesters and polycarbonates Several methods have been developed to prepare polyesters and polycarbonates. The best method consists in the ring-opening polymerisation (ROP) of a cyclic monomer, selected either from a 4- to 6-membered lactone, lactide or cyclic carbonate monomer. These ROP reactions are usually carried out in the presence of an organometallic catalyst, which allows access to polymers with high activity, controlled molar mass, molar mass distribution and especially to polymers with controlled stereochemistry.
  • ROP ring-opening polymerisation
  • organometallic catalyst are currently based on metals such as magnesium, calcium, iron, zinc or group 3 (including the lanthanide serries) elements, as described for instance in M. Okada ( M. Okada, Prog. Poly. Sci. 2002, 27, 87-133 ), in H. Yasuda ( H. Yasuda, J. Organomet. Chem. 2002, 647, 128-138 ), in Kerton et al. ( F. M. Kerton, A. C. Whitwood, C. E. Williams, Dalton Trans. 2004, 2237-2244 ), in Hou and Wakatsuki ( Z. Hou, Y. Wakatsuki, Coord. Chem. Rev. 2002, 231, 1-22 ), and in Agarwal et al. ( S. Agarwal, C. Mast, K. Dehnicke, A. Greiner, Macromol. Rapid Commun. 2000, 21, 195-212 ).
  • metals such as magnesium, calcium, iron, zinc or group 3
  • Z(R 2 ) 3 can also be a substituted aryl group, wherein M is a metal Group 3 of the periodic Table or a member of the lanthanide series, wherein R $ is alkyl, CH 2 SiMe 3 , CH(SiMe 3 ) 2 , or OR* wherein R* is alkyl, aryl or lactate O-CH(CH3)(COOR'), or NR**2 wherein R** is SiMe 3 or SiHMe 2 .
  • R $ is N(SiHMe 2 ) 2 , N(SiMe 3 ) 2 or O i Pr.
  • R 1 , R 3 , R 4 , R 5 , R 6 and R 7 are each independently selected from hydrogen or alkyl groups having at most 6 carbon atoms, more preferably they all are hydrogen.
  • Z' is S or N.
  • Z is C or Si more preferably, it is Si.
  • R 2 is a substituted or unsubstituted phenyl group, or a higher aromatic group (e.g. naphthyl), or an alkyl. More preferably, it is an unsubstituted phenyl group or a tertio-butyl group.
  • inert functional group is meant a group, other than hydrocarbyl or substituted hydrocarbyl, that is inert under the complexation conditions to which the compound containing said group is subjected.
  • They can be selected for example from halo, ester, ether, amino, imino, nitro, cyano, carboxyl, phosphate, phosphonite, phosphine, phosphinite, thioether and amide.
  • halo such as chloro, bromo, fluoro and iodo, or ether of formula - OR* wherein R* is unsubstituted or substituted hydrocarbyl.
  • the metal complex of formula I results from the complexation reaction of metallic salt MR $ n with pro-ligand II in a solvent
  • the Group 3 metal and lanthanide complexes are used in the ring-opening polymerisation.
  • R'OH an hydrocarbyl, linear or branched, having from 1 to 20 carbon atoms.
  • R' is a secondary alkyl residue or benzylic group, more preferably it is isopropyl ( i Pr) or benzyl (Bn).
  • alcohol acts as a reversible transfer agent it is observed that as the ratio alcohol/metal increases, the molecular weight of the polymer chains decreases to the same extent.
  • the molecular weight of the polyester, polylactide or polycarbonate also depends upon the nature of the alcohol.
  • the alcohol can contain a functional group which will be selectively capped at the terminus of each polyester, polylactide or polycarbonate chain.
  • This functional group can be used for various purposes. As non-limitating examples, one can cite:
  • Polymerisation can be carried out in bulk (liquid or in melt) or in solution. Usual aromatic and aliphatic hydrocarbons can be used for that purpose.
  • Polymerisation is conducted at a temperature ranging from 20 °C to 180 °C, preferably between 50 and 150 °C.
  • the pressure ranges from 0.5 to 20 atm, preferably it is 1 atm.
  • the polymers thus prepared show typically a unimodal molecular weight distribution that ranges from 1.1 to 5.0, more typically from 1.5 to 2.5.
  • the number average molecular weight Mn can be tuned by the monomer-to-alcohol ratio and ranges from 1 000 to 1 000 000 g/mol, more typically from 10 000 to 250 000 g/mol.
  • This polymerisation process is operative for 5- to 7-membered cyclic carbonates, 4-to 7- membered lactones, 6-membered lactides or combinations thereof.
  • lactide all stereoisomers or mixtures of those
  • beta-butyrolactone trimethylenecarbonate (TMC)
  • 2-benzyloxy-trimethylenecarbonate BTMC
  • 2-hydroxy-trimethylenecarbonate TMCOH
  • BDMC 4-(benzyloxymethyl)-1,3-dioxolan-2-one
  • DMCOH 4-(hydroxymethyl)-1,3-dioxolan-2-one
  • OTMC 2-oxy-trimethylenecarbonate
  • DTMC dehydrotrimethylenecarbonate
  • Copolymers resulting from any combinations of these monomers are also included in the present invention.
  • the reaction mixture was heated at reflux for a period of time of 20 h, cooled and diluted with 500 mL of water.
  • the organic part was extracted with 3 times 50 mL of Et 2 O.
  • the combined organic extracts were dried over MgSO 4 , and evaporated.
  • the crude residue was recrystallised from heptane and dried under vacuum to give 7.11 g of (3-methoxy-2-naphthyl)(triphenyl)silane (17.07 mmol) with a yield of 90 %.
  • This is a one pot method comprises the following steps:
  • Precursor P1 is meso - ⁇ ONO ⁇ La[N(SiHMe 2 ) 2 ](THF)
  • Precursor P2 was in situ generated from ⁇ ONO ⁇ H 2 and Y[N(SiHMe 2 ) 2 ] 3 (THF) 2
  • Precursor P3 is meso - ⁇ OSO ⁇ La[N(SiHMe 2 ) 2 ](THF)
  • Precursor P4 was in situ generated from ⁇ OSO ⁇ H 2 and Y[N(SiHMe 2 ) 2 ] 3 (THF) 2
  • the polymerisation was carried out as follows:
  • Precursor P1 is meso - ⁇ ONO ⁇ La[N(SiHMe 2 ) 2 ](THF)
  • Precursor P2 was in situ generated from ⁇ ONO ⁇ H 2 and Y[N(SiHMe 2 ) 2 ] 3 (THF) 2
  • Precursor P3 is meso - ⁇ OSO ⁇ La[N(SiHMe 2 ) 2 ](THF)
  • Precursor P4 was in situ generated from ⁇ OSO ⁇ H 2 and Y[N(SiHMe 2 ) 2 ] 3 (THF) 2
  • the polymerisation was carried out as follows:

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
EP08290186A 2008-02-25 2008-02-25 Group 3 post-metallocene complexes based on bis (Naphthoxy)pyridine and bis (Naphthoxy) thiophene ligands for the ring-opening polymerisation of polar cyclic monomers Withdrawn EP2093242A1 (en)

Priority Applications (9)

Application Number Priority Date Filing Date Title
EP08290186A EP2093242A1 (en) 2008-02-25 2008-02-25 Group 3 post-metallocene complexes based on bis (Naphthoxy)pyridine and bis (Naphthoxy) thiophene ligands for the ring-opening polymerisation of polar cyclic monomers
CN2009801064101A CN101959928B (zh) 2008-02-25 2009-02-17 用于极性环状单体的开环聚合的基于双(萘氧基)吡啶和双(萘氧基)噻吩配体的第3族后茂金属络合物
EP09714063A EP2247641A1 (en) 2008-02-25 2009-02-17 Group 3 post-metallocene complexes based on bis(naphthoxy)pyridine and bis(naphthoxy)thiophene ligands for the ring-opening polymerisation of polar cyclic monomers
KR1020107018747A KR101217954B1 (ko) 2008-02-25 2009-02-17 극성 시클릭 단량체의 개환 중합을 위한 비스(나프톡시)피리딘 및 비스(나프톡시)티오펜 리간드 기재의 ３ 족 포스트-메탈로센 착물
US12/919,256 US8436133B2 (en) 2008-02-25 2009-02-17 Group 3 post-metallocene complexes based on bis(naphthoxy)pyridine and bis(naphthoxy)thiophene ligands for the ring-opening polymerisation of polar cyclic monomers
BRPI0907927-0A BRPI0907927A2 (pt) 2008-02-25 2009-02-17 Complexos de pós-metaloceno do grupo 3 com base em ligantes bis(naftóxi)piridina e bis(naftóxi)tiofeno para a polimeração por abertura de anel de monômeros cíclicos.
EA201070998A EA018583B1 (ru) 2008-02-25 2009-02-17 Пост-металлоценовые комплексы 3 группы на основе бис(нафтокси)пиридиновых и бис(нафтокси)тиофеновых лигандов для полимеризации с разрывом кольца полярных циклических мономеров
PCT/EP2009/051869 WO2009106459A1 (en) 2008-02-25 2009-02-17 Group 3 post-metallocene complexes based on bis(naphthoxy)pyridine and bis(naphthoxy)thiophene ligands for the ring-opening polymerisation of polar cyclic monomers
US13/847,215 US20130281681A1 (en) 2008-02-25 2013-03-19 Group 3 Post-Metallocene Complexes Based on Bis(Naphthoxy)Pyridine and Bis(Naphthoxy)ThioPhene Ligands for the Ring-Opening Polymerisation of Polar Cyclic Monomers

Applications Claiming Priority (1)

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EP08290186A EP2093242A1 (en) 2008-02-25 2008-02-25 Group 3 post-metallocene complexes based on bis (Naphthoxy)pyridine and bis (Naphthoxy) thiophene ligands for the ring-opening polymerisation of polar cyclic monomers

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EP08290186A Withdrawn EP2093242A1 (en) 2008-02-25 2008-02-25 Group 3 post-metallocene complexes based on bis (Naphthoxy)pyridine and bis (Naphthoxy) thiophene ligands for the ring-opening polymerisation of polar cyclic monomers
EP09714063A Withdrawn EP2247641A1 (en) 2008-02-25 2009-02-17 Group 3 post-metallocene complexes based on bis(naphthoxy)pyridine and bis(naphthoxy)thiophene ligands for the ring-opening polymerisation of polar cyclic monomers

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US (2) US8436133B2 (ko)
EP (2) EP2093242A1 (ko)
KR (1) KR101217954B1 (ko)
CN (1) CN101959928B (ko)
BR (1) BRPI0907927A2 (ko)
EA (1) EA018583B1 (ko)
WO (1) WO2009106459A1 (ko)

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CN109843971A (zh) * 2016-06-24 2019-06-04 阿科玛法国公司 包含可生物降解的聚酯嵌段的纳米结构化的嵌段共聚物膜

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EP2093229A1 (en) * 2008-02-25 2009-08-26 Total Petrochemicals Research Feluy Post-metallocene complexes based on bis(naphtoxy) pyridine and bis(naphtoxy) thiophene ligands for the polymerisation of ethylene and alpha-olefins
EP2307478B1 (en) * 2008-07-31 2013-11-20 Total Research & Technology Feluy Catalytic process for polymerising cyclic carbonates issued from renewable resources.
WO2012038240A1 (en) * 2010-09-21 2012-03-29 Total Petrochemicals Research Feluy One-step, one-pot process for preparing multiblock and gradient copolymer
CN102633824B (zh) * 2012-03-13 2015-04-22 山西出入境检验检疫局检验检疫技术中心 一种含有吡啶基团的三齿有机铝化合物及其合成方法
US9394387B2 (en) 2014-05-15 2016-07-19 Chevron Phillips Chemical Company Lp Synthesis of aryl coupled bis phenoxides and their use in olefin polymerization catalyst systems with activator-supports
CN113968884B (zh) * 2021-10-26 2022-07-19 大连理工大学 一种新型双磷酰胺稀土金属配合物、制备方法及催化聚合应用

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1911935A (zh) * 2006-08-25 2007-02-14 中国科学院长春应用化学研究所 催化丙交酯立体选择性聚合稀土配合物

Family Cites Families (2)

* Cited by examiner, † Cited by third party
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DE10113302B4 (de) * 2001-03-19 2009-09-24 Fraunhofer-Gesellschaft für die angewandte Forschung e.V. Verfahren zur Herstellung von Homo- und Copolyestern der Milchsäure
US6825296B2 (en) * 2002-03-29 2004-11-30 The University Of Hong Kong Catalyst component for olefin polymerization

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1911935A (zh) * 2006-08-25 2007-02-14 中国科学院长春应用化学研究所 催化丙交酯立体选择性聚合稀土配合物

Non-Patent Citations (11)

* Cited by examiner, † Cited by third party
Title
B. J. O'KEEFE; M. A. HILLMYER; W. B. TOLMAN, J. CHEM. SOC. DALTON TRANS., 2001, pages 2215 - 2224
DATABASE WPI Week 200745, Derwent World Patents Index; AN 2007-460011, XP002490012 *
F. M. KERTON; A. C. WHITWOOD; C. E. WILLIAMS, DALTON TRANS., 2004, pages 2237 - 2244
H. YASUDA, J. ORGANOMET. CHEM., vol. 647, 2002, pages 128 - 138
J. WU ET AL., COORD. CHEM. REV., vol. 250, 2006, pages 602 - 626
M. OKADA, PROG. POLY. SCI., vol. 27, 2002, pages 87 - 133
O. DECHY-CABARET; B. MARTIN-VACA; D. BOURISSOU, CHEM. REV., vol. 104, 2004, pages 6147 - 6176
S. AGARWAL ET AL., MACROMOL. RAPID COMMUN., vol. 21, 2000, pages 195 - 212
YU CUIPING ET AL: "Ring-opening polymerization of 2,2-dimethyltrimethylene carbonate using rare earth tris(4-tert-butylphenolate)s as a single component initiator", 2 April 2004, J. MOL. CATAL. A CHEM.; JOURNAL OF MOLECULAR CATALYSIS A: CHEMICAL APR 2 2004, VOL. 212, NR. 1-2, PAGE(S) 365 - 369, XP002490011 *
YU TE-LIANG ET AL: "Catalysts for the ring-opening polymerization of epsilon -caprolactone and L-lactide and the mechanistic study", POLYMER; POLYMER JUL 25 2005, vol. 46, no. 16, 25 July 2005 (2005-07-25), pages 5909 - 5917, XP002490010 *
Z. HOU; Y. WAKATSUKI, COORD. CHEM. REV., vol. 231, 2002, pages 1 - 22

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109843971A (zh) * 2016-06-24 2019-06-04 阿科玛法国公司 包含可生物降解的聚酯嵌段的纳米结构化的嵌段共聚物膜

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EA018583B1 (ru) 2013-09-30
KR101217954B1 (ko) 2013-01-02
EA201070998A1 (ru) 2011-02-28
BRPI0907927A2 (pt) 2015-07-28
US20110112273A1 (en) 2011-05-12
WO2009106459A1 (en) 2009-09-03
US8436133B2 (en) 2013-05-07
CN101959928A (zh) 2011-01-26
KR20100115771A (ko) 2010-10-28
US20130281681A1 (en) 2013-10-24
CN101959928B (zh) 2012-08-08
EP2247641A1 (en) 2010-11-10

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